EPA-600/4-77-017
                                                     April 1977
                REGIONAL AIR POLLUTION STUDY

Sulfur Compounds and Particulate Size Distribution Inventory
                             by
                       Fred E. Littman
                      Robert W. Griscorn
                         Harry Wang
                    Air Monitoring Center
                   Rockwell International
                   Creve Coeur, MO  63141
                     Contract 68-02-1081
                        Task Order 56

                       Project Officer

                  Francis A. Schiermeier
               Regional Air Pollution Study
        Environmental Sciences Research Laboratory
                11640 Administration Drive
                  Creve Coeur, MO  63141
        ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
            OFFICE OF RESEARCH AND DEVELOPMENT
           U.S. ENVIRONMENTAL PROTECTION AGENCY
       RESEARCH TRIANGLE PARK, NORTH CAROLINA  27711

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                                  DISCLAIMER

     This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recommendation for use.
                                      11

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                                   ABSTRACT

     In conjunction with the Regional Air Pollution Study being conducted
in the St. Louis Air Quality Control Region  (AQCR), a methodology for
estimating the amount of sulfur trioxide  (SO ) emitted by combustion sources
was developed. It is based on SO /SO  ratios determined both experimentally
and from literature surveys.  The most likely value appears to be 1.85% of
the SO  emissions.  On this basis, about 22,000 tons of SO  are emitted
yearly from combustion sources.

     A fine particle size inventory for the area was also developed.  The
inventory gives a breakdown of particulate emissions in the range of 7 to
.01 microns, based on production rates and collection efficiencies for
point sources in the St. Louis AQCR.  The information on the SO /SO
ratios and the particle size breakdown is stored in the RAPS Data Handling
System.
                                      111

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                                   CONTENTS

Abstract	iii
Figures	   vi
Tables	vii

1.0  Summary	    1

2.0  Introduction 	    2

3.0  Sulfur Compounds 	    3

     3.1  Scope and Definitions 	    3
     3.2  Development of Base Data and Algorithms	    3

          3.2.1     Base Data	    3
          3.2.2     Sulfur Dioxide-Sulfur Trioxide Ratios 	    4

4.0  Particulate Size Inventory	   12

     4.1  Definitions and Scope of Inventory	   12
     4.2  Development of Inventory for AQCR-70	   13

          4.2.1     Method	   13
          4.2.2     Particulate Size Inventory Data Files	   15

     4.3  Experimental Particle Size Distribution Data	   15

          4.3.1     Method and Equipment	   16
          4.3.2     Measurements of Particle Size	   16

References	   26
Appendices
     I.   Laboratory Evaluation of the "Shell" Method of
          Determination of S03	    29

    II.   Particulate Inventory: Size - File	    42

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                                    FIGURES
Number                                                                Page
1         SCL Concentration Plotted Aganist 0? in Flue
          Gas for Four Star Coal.	5
2         Variation of SCL Conversion to SCL with Oxygen	6
3         Percentage Conversion of SCL to SCL	9
4         Sulphur Trioxide Collector	10
5         Anderson Stack Sampler	17
6         Deposits on Stage 2 - General Motors	20
7         Deposits on Stage 4 - General Motors	20
8         Deposits on Stage 6 - General Motors	20
9         Deposits on Stage 2 - Stag Brewery	21
10        Deposits on Stage 4 - Stag Brewery	21
11        Deposits on Stage 6 - Stag Brewery	21
12        Deposits on Back-up Filter - Stag Brewery	21
13        Ammonium Sulfate Crystals on Back-Up Filter -
          General Motors	23
14        Particle Size Distribution Wood River Boiler #4  	 25
                                      VI

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                                    TABLES



Number                                                                Page



1          Relationship Between Boiler Size  and  SO.,  Formation	6



2         Sulfur Oxide Analysis and Ratios  	   8



3         Particle Size Distribution Results 	  18
                                     vn

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                          1.0  SUMMARY

     A methodology for estimating the amount of sulfur trioxide (SO.,) emitted
by combustion sources in the St.  Louis AQCR was developed.  It is based on S0?/
S03 ratios determined both experimentally and from literature surveys.   The most
likely value appears to be 1.85% of the S02 emissions.  On this basis,  about
22,000 tons of SO^ are emitted yearly from combustion sources.
     An alternative method for SO., determination was evaluated and field tested.
The "Shell" method, developed originally by Goks0yr and Ross, appears to give
reliable results both in the laboratory and in the field.
     A fine particle size inventory for the area was developed, based on earlier
work by MRI.  The inventory gives a breakdown of particulate emissions  in the range
of 7 to .01 microns, based on production rates and collection efficiencies for
point sources in the St. Louis AQCR.  The information can be stored in  the RAPS
Data Handling System.
     Experimental data were obtained on particle size distribution  of  represen-
tative sources using an Andersen cascade impactor.  The results indicated a
bimodal distribution peaking at around 5 microns and at less than 7 microns.
                                   -1-

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                       2.0  INTRODUCTION

     Within the framework of the Regional  Air Pollution Study (RAPS)  at  St.  Louis,
MO., a high-resolution emission inventory  has been assembled.   Initially,  this
inventory was focused on one pollutant - sulfur dioxide -  for which  hourly,
measured emission data were collected.  This inventory was broadened  to  include
all  "criteria" pollutants.  In addition, special  inventories  were  also developed
for trace pollutants, heat emissions and hydrocarbons.
     This study is concerned with two classes of pollutants:   sulfur  compounds -
primarily SO  (sulfur trioxide) since a detailed S02  (sulfur  dioxide)  inventory
exists, and a particle size inventory, a refinement of the particle  inventory
available as part of the "criteria"  pollutant inventory, which does  not  take
particle size into consideration.
                                    -2-

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                      3.0  SULFUR COMPOUNDS

     Hourly, measured emission data for all major point sources of S0? in the St.
Louis AQCR have been gathered and are available in the RAPS emission inventory
                                                          (1-4)
data base.  This work is described in a series of reports v   '.
     In the St. Louis area, virtually all  sulfur dioxide emissions (98+%) occur
from point sources (stacks, vents, etc.).   This is not to say that the remaining
emissions are unimportant, since they originate essentially at street level  (auto-
motive emissions, residential and commercial  heating etc.) and thus may contribute
a disproportionate share to ambient concentrations.

3.1  SCOPE AND DEFINITIONS
     This report deals with SO, emissions  from stationary point sources.   The term
"sulfur trioxide" (SO.J is used, though it is realized that in its particulate
form, in which it is customarily collected, the compound is hydrated to sulfuric
acid (H2S04).
     At stationary point sources, both SO- and SO, originate from the oxidation
of sulfur or sulfur containing compounds.   The bulk of the sulfur oxides  orig-
inates from the combustion of fossil  fuels, while the remainder comes from pro-
cess operations such as the roasting of ores, the manufacture of sulfuric acid,
etc.
     The two oxides exist side by side in  an  equilibrium which is largely de-
termined by operational conditions at the  source.  The amount of SCU present is
usually expressed as a fraction of the SOo concentration.

3.2  DEVELOPMENT OF BASE DATA AND ALGORITHMS
3.2.1  Base Data
     In conformity with the National  Emission Data System (NEDS)  ^5',  the RAPS
Emission Inventory records basic fuel  consumption and process data, rather than
mass emissions of pollutants.  The basic data are converted to mass flow  of pol-
lutants using emission factors, stored in  a separate file.  The advantage of this
                                    -3-

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arrangement is that it permits periodic updating of the relatively small  emis-
sion factor file, without disturbing the large mass of base data.
     NEDS is an annual system, based on yearly reports gathered by local  or re-
gional  Air Pollution Control  Agencies.   By contrast, the RAPS emission inventor
which covers the St. Louis Interstate Air Quality Control  Region,  is a collec-
tion of hourly values obtained directly for this purpose.   Hourly  data, based 01
a measured parameter such as  fuel  consumption, steam or power production  are
being obtained from all  the major sources of pollutants in the AQCR.  A major
source for the purposes  of this inventory, is one which individually emits more
than 0.1% of the total of a given "criteria" pollutant in  the area.  "Criteria"
pollutants for which national standards exist include SCLj NCL, CO, hydrocarbon:
and particulates.
     The RAPS Emission Inventory also contains data on smaller sources, emitting
as little as 10 tons of S0? per year.  Data on these sources are based on annua"
consumption or process figures, modified by an operating pattern peculiar to the
source.  The pattern, which is also stored in the RAPS Data Handling System,
recor''0 the hcpirs per day and days per week for normal operation,  as well as an:
holiday or vacation periods.   Using this information, average hourly S02 emis-
sion values can be obtained as an output.  Since these sources make up less thai
2% of all point source emissions, no significant errors are introduced by this
method.
     As a result of this effort, a detailed and relatively accurate record of
SOp production exists, which can serve as a base for an SO., inventory.

3.2.2  Sulfur Dioxide - Sulfur Trioxide Ratios
     In the presence of excess air in a combustion operation, a fraction of the
sulfur dioxide is converted to sulfur trioxide (SO.J according to

                 2 S02 + 02 -»- 2 S03 + 45.2 Kcal
     The reaction is exothermic; however, the reaction rates are negligible be-
low 200°C (392°F), reach a maximum around 400°C (752°F) and taper off  to zero a~
1000 C (1832 F).  Rapid conversion takes place only in the presence of a catalys
                                    -4-

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As would be expected from the reaction constant
                       K = (S02)2  x  (02)
the yield increases with excess oxygen.
     The information of SO, in boiler stack gases has been investigated fairly
                      / r \  O
extensively.  Corbett     investigated the SCL formation in an oil-fired boiler.
He found that 1  to 3% of the S0~ was oxidized to SO^.  The amount of SCU found
did not correlate with the percentage of sulfur in the oil or boiler conditions.
Lee ^  ' used a wet-bottom, pulverized coal-fired research boiler, several  types
of coal, and varied the excess oxygen from 0.5 to 5%.  He found a distinct re-
lationship on excess oxygen (Fig. 1).
                              V  =
                                          SO   6-0
                                                   7O   8-O
FIGURE 1:  S02 CONCENTRATION PLOTTED AGAINST 02 IN FLUE GAS FOR FOUR STAR COAL
                                 (Ref.  7)
                                    -5-

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                      (8)
     In a later study v  ' Lee obtained similar  results  in  an  oil-fired furnace.

      (9)
Gills v ' found a similar dependence on excess  oxygen,  but did  not get a flat-


tening of the curve up to 12% oxygen (Fig.  2).   He  also found a strong de-


pendence on boiler size, with an 850 tons steam/hour  boiler producing a 1% con-


version to S03 at an oxygen level of 0.5%,  while smaller boilers (up to 25 tons


steam/hour) produce only a 0.25% conversion under similar  conditions.
 o
 o
 X


^
 en
 •+• i

 61
                  2-0
                   1-0
                c/i
                tr
                  O-5
                O
                o
                     BOILER CAPACITIES

                     UP TO 25 tons steam/h
                    O    2   4   6    8   1O

                     OXYGEN CONTENT (% VOL)
                              12
Figure 2:  VARIATION OF S02 CONVERSION TO S03 WITH OXYGEN  (Ref.  9)




     The latter relationship was confirmed  by Reese  ^   ',  who  obtained the


following results at 4% excess oxygen.
                               TABLE 1
         RELATIONSHIP BETWEEN BOILER SIZE AND SO,  FORMATION
Instal




lation size
MW
55
no

% Conversion '.
to
2
3

185 1 4
SO^
.1
.5

.4
i

i
I
.J
                                     -6-

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     In general, the percentage conversion falls in the range of 0.5 to 5%, with
absolute values below 50ppm of SCL*.
     Our results are shown in Table 2 and Figure 3.
     The concentration of S02 varied  from 120 ppm for a boiler operated on
distillate oil to 2660 ppm S0? for a  coal burning boiler.   Average for coal burn-
ing boilers was about 1600 ppm.  The  SO^ concentration ranged from 2.7 to 44.3
ppm, well  within the range indicated  by other investigators.   As indicated in
Figure 3,  there appears to be a marked dependence on excess oxygen.  The percent-
age of S0~ increased with increasing  oxygen up to about 9%, then dropped rapidly.
This may be due to the cooling effect of large amounts of excess air.   There did
not seem to be any correlation with the sulfur content of the fuel nor did there
appear to  be any marked effect of boiler capacity on the amount or concentration
of SO., produced.
     The RMS average S03 emission appears to be about 1.85% of the S02 emission.
This factor will be incorporated in the data handling system output program,
which will report SO^ emissions based on the corresponding S02 emissions.  Using
the current figures for SCL, this amounts to an annual  emission of 22,585 tons
of SO^ per year.
Analytical Methods for S03

     The current standard method for  SO., in stack gases is EPA Method  8 (CFR
40, 60.85, Appendix-Test Methods).  In this method, the sample of stack gases
is drawn through a series of impingers.  The first impinger contains 100ml  of
80% iso-propanol; the second and third 100ml of 3% hydrogen peroxide.   There is
a filter between the first and second impinger to retain entrained particulates.
The contents of the impingers are analyzed for sulfate using the barium
perchlorate-thorin method.

                                               (9)
*  An interesting exception was found by Gills v '  in brick kilns, where  up to
   28% of  the sulfur oxides were in the form of SO.
                                    -7-

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°7o S03

   3-1
    2 _J
   0
               2       4
8      10      12    °7o 02
                                    FIGURE  3
                      PERCENTAGE  CONVERSION OF S02 TO S03
                                      -9-

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     Recent work cast doubts on both accuracy and reproducibility of Method
8^   .   The method assumes that only SO, (sulfuric acid mist) will be  retained
in the  first impinger and the filter (both of which are analyzed together).
                    (12)
However, Hillenbrand^  ' found that substantial amounts of SCL are retained  in
the first impinger, some of which is subsequently oxidized to SO.,, thus  con-
tributing to high results.  For this reason a different technique was  used,
                                              (13)
which was first described by Goks0yr and Rossv    and  subsequently verified  by
                      (14)
Lisle and Sensenbaugh     .   The method is generally referred to as the  "Shell"
method, as it was developed in their laboratories.  The method is based  on the
condensation of sulfuric acid mist at temperatures below  its dew point (but
above the dew point of water) in a condenser  backed up by a fritted glass  fil-
ter (Fig. 4).  The condensate is washed out and titrated.
                                              STOPPER
                      GRADE 4
                      S.MERED
                       GLASS
                       DISC
            FIGURE 4: SULPHUR TRIOXIDE  COLLECTOR  (Ref.  12)
                                     -10-

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     Data presented in references 12 and 13 indicate that adsorption  of S03
is essentially complete,  repeatability is excellent, S0? in  concentrations
                                                    4.  ^
up to 2000ppm does not interfere and a precision  of - O.Sppm of SCL can be
readily attained.
     The method was then evaluated in  our laboratories.   The  results  of the
evaluation are shown in Appendix I; they indicate an  average  100.1  -  6.5%
recovery with no significant interference from any of the variables tested.
                                    -11-

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                    4.0  PARTICULATE  SIZE  INVENTORY

     Emissions of participate materials constitute  a more complex problem
than gaseous emissions,  since the properties of particles are determined
not only by their composition, but also by their size and shape.   In  fact,
the most important properties of particles, their effect on  visibility,
their life-time as suspended materials, and to a large extent, their  effect
on health, are all determined by particle size.   On all  of these  counts  small
particles, 5 microns or  less in diameter, are responsible for most of the ob-
served effects.
     The common methods  of collection and reporting of particulate emissions
do not distinguish particle size.  Total  particulate matter is reported  on a
weight basis, which biases the results in favor of  large particles.  Since large
particles are only of local  importance -  they settle out rapidly  - and are  gen-
erally not involved in health effects because they  are readily retained  by  the
body's screening mechanisms, there are good reasons why particulate emission
data should be reported  in such a way as  to provide maximum information  on  small
particles.

4.1  DEFINITIONS AND SCOPE OF INVENTORY
     There is no universally accepted definition of "fine particles", but most
authors agree on a range of 3 to 5 microns as the upper limit.  Particles small-
er than approximately 5  microns have settling velocities in still air of the
order of 0.01 cm/sec and tend to stay aloft almost  indefinitely.   Particles can
be either solid or liquid.
     The most up-to-date study of fine particulate  emissions is contained in EPA
Technical  Report entitled "Fine Particulate Emission Inventory and Control
Survey" ^   .  The methodology contained  in that report was  applied to the St.
Louis AQCR.  In addition, samples were taken at representative emission  sources
using an Andersen cascade impactor.   Data developed from this study are  also
included.
                                     -12-

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4.2  DEVELOPMENT OF INVENTORY FOR AQCR-70
     In order to prepare a particle size inventory within the scope of RAPS,
compatible with the NEDS and RAPS Data Handling Systems,  the procedure outlined
below was used.  No effort was devoted to the inventory of area sources,  mobile
sources, chemical  and physical characterization of these  particulates.

4.2.1  Method
     The method put forth in the "Fine Particulate Emission Inventory and Control
Survey" uses the following equation for the calculation of particulate emissions:
        r         PefCf                                                    n
         drd2   =         *
where

      d-j-d^ = emission rate for particles with diameter between d,  and d~

     P      = production rate
     ef     = emission factor (uncontrolled)

     C,      = percentage of production capacity on which control  equipment is in-
              stalled (for that device)
     f-j(d)  = emitted particle size distribution

     f~(d)  = penetration = (1 -fractional efficiency of control system)

The size ranges are (in microns):
     .01 - .05, .05- .1, .1  - .5, .5-1, 1  -3,  3-7.

The data sources are:

     (1)  RAPS coding forms (or NEDS computer listing)
     (2)  "NEDS Source Classification Codes and Emission Factor Listing"  (SCC
          listing), July 1974.
     (3)  "Fine Particulate Emission Inventory and Control  Survey"  (EPA-450/3-
          74-040), January 1974.

The equations used for calculating the total  particulate emissions  are:

     E,   , (total)  =  E,  .  (controlled)     E,   , (uncontrolled)    (2)
      Q-i ~UQ             UT~UO              '    Q -i ~" Q^

                                    -13-

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     where E^ _^  (controlled) is expressed in equation 1, and
                                   Pe (1-Ct}
           E, _,  (uncontrolled)  =   f        * f  (d]
            Q]  °2                    2000       rl  (Q)
     The assumption  used here is  that f~ (d)  applies  to that  fraction of the
emission which  is specified by C.  and 0-C.)  has  no control  and therefore
f2(d) = I-
     The algorithm for a computer program may be  something like the following:
       I  For every  point source
      la  Look up from RAPS coding form, the  SCC  code          Card 4
      Ib  Look up P  (annual data)                               Card 5
      Ic  Look up C.  (control efficiency)                      Card 3
      Id  Look up CID (control device ID code)                 Card 3
      II  From EFACTR file.  Look up e,. (uncontrolled emission factor) for the
          corresponding SCC number.
     Ill  From SIZE  file.  Look up size distribution in fractional  values for each
          size  range for the corresponding SCC number.
      IV  From the EFCNCY file.  Look up the  fractional efficiency of each size
          for the corresponding control device as identified  by the code number
          CID.
       V  Calculate  the emissions using equations 1, 2  and 3.
The following are examples of the three computer input data files:
File Name:  SIZE
     SCC Code   .01-.05    .05-.1    .1-.5   .5-7   1-3   3-7
                              Fractional  Values

File Name:  EFACTR
     SCC Code      Emission Factor
                   Pounds per Ton

                                     -14-

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File Name:  EFCNCY

     CID   .01-.05   .05-.1   .1-.5   .5-.1    1-3   3-7
                          Efficiency

4.2.2  Particulate Size Inventory Data Files
     Of the three files required for calculations of the particulate size inven-
tory, one, the emission factor file EFACTR, is already contained in the RAPS in-
ventory.  The other two were developed on this Task and are given in Appendix II.
     The SIZE-file, in a matrix form, gives the particle-size distribution of
emitted particulates for any one of the forty-four SCC-codes listed in column 2.
Each column between columns 3 through 8 lists the fractional value of the total
particulate effluent that falls within the corresponding particle-size range.
     All values  to the right of the double line (columns 2-8) are keypunched for
computer input with the READ format: (18, 6F4.0), blanks = 0.  The fractional
values in the F-format are left justified with no decimal points.
     The EFCNCY-file lists the fractional efficiency of the effluent control de-
vice for each particle-size range.  The control device is identified by the CID
number under column 2 and the particle-size ranges have the same diameter group-
ings as that in  the SIZE-file.
     All values  to the right of the double line (columns 2-8) are keypunched for
computer input with the READ format:
                        (13, 6F4.0), blanks = 0
The fractional  values in the F-format are left justified with no decimal points.
     Both files  were keypunched.  The cards are available for input into the RAPS
Data Handling System.

4.3  EXPERIMENTAL PARTICLE SIZE DISTRIBUTION DATA
     In connection with the emission factor verification program carried out as
part of the RAPS  study, data were gathered on particles size distribution of a
number of representative sources.
                                     -15-

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4.3.1   Method and Equipment
     Particle size testing was  performed with an  Andersen  Stack  Sampling  head
coupled with the apparatus used for standard EPA  method for particulates.   The
Andersen is a fractionating inertial  impactor which  separates  particles  accord-
ing to aerodynamic characteristics.
     The Mark II sampling head  consists  of a stainless  case,  plate  holder and
nine jet plates.  The plates have a pattern of precision-drilled orifices.   The
nine plates, separated by 2.5 millimeter stainless  steel  spacers, divide  the
sample into eight fractions or  particle  size ranges.   The  jets on each plate are
arranged in concentric circles  which are offset on  each succeeding  plate.   The
size of the orifices is the same on a given plate,  but is  smaller for each
succeeding downstream plate. Therefore, as the sample is  drawn  through  the
sampler at a constant flow rate, the jets of air  flowing through any particular
plate direct the particulates toward the collection  area on the  downstream plate
directly below the circles of jets on the plate above.   Since  the jet diameters
decrease from plate to plate, the velocities increase such that  whenever the
velocity imparted to a particle is sufficiently great,  its inertia  will  overcome
the aerodynamic drag of the turning airstream and the particle will be impacted
on the collection surface.
     The Mark III is identical  to the Mark II except the location of the  orifices
in the plates have been modified to permit the use  of a special  collection sub-
strate (glass fiber in our tests).  This permits  lighter tare  of weights  for
gravimetric analyses and a collection of material for chemical analysis.   Figure
5 illustrates the Andersen sampling head and an exploded view  of the plate holder
and plates.

4.3.2  Measurements of Particle Size
     Particle Size Distribution measurements have been conducted at five of the
seven test sites sampled in 1975.  Initially only the Andersen Mark II plates
were available.  Because of this the only results available at the first test
site are the weight distribution.  On subsequent  tests, runs were made with both
the Mark II plates and Mark III plates with glass fiber filters  for comparison.
Sites that have been tested for particle size are shown in Table 3.  Some of the
filter samples were inspected microscopically and a few of these were also
                                     -16-

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AIR FLOW
0
                         FIGURE 5
                  ANDERSEN  STACK SAMPLER
                             -17-

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analyzed by x-ray fluorescence.   A summary of the results of the testing is given
in Table 3.  Particle size is given as aerodynamic size for spherical  particles
with unit density.
                             TABLE 3
                 PARTICLE SIZE DISTRIBUTION RESULTS
Source

111. Power - Wood River
Highland Electric
Stag Brewery
General Motors
Amoco

Sec Code

1-01-002-02
1-01-002-08
1-02-002-05
1-02-002-09
3-06-001-02
3-06-001-03

>7y
22.5
26.6
37.4
14.3
13.9

% vs
3-7y
22.8
18.9
16.0
24.4
8.9

Parti cl
1-3U
18.5
10.0
7.6
18.5
22.0

e Size
0.5-lvi
8.3
12.7
18.3
9.2
18.8


< 0.5u
27.9
31.8
20.7
33.6
36.4

     At General Motors, fourteen tests were performed to evaluate variations of
testing methods consisting of placing the Andersen in-stack, out of stack (in oven)
using Mark II plates and Mark III plates with filters.  Each of these methods has
its advantages which may make it desirable for any one individual test.  The main
objective of these tests was to arrive at a testing arrangement to be used on all
subsequent tests.  As it turned out there was no clearcut single method which
proved better than the others.
     Sampling in the stack avoids any problems with extracting a sample and hav-
ing some of it deposited in the probe.  Also the sample head is at the same temper-
ature as the stack gases which avoids any problems of condensation.  In-stack samp-
ling, however, means the impaction surface is vertical and is subject to having
the sample dislodged in handling.  When sampling must be done vertically in a duct,
from the top down, this method cannot be used.
     Sampling with the Andersen sampler in the sample oven at the end of a heated
probe affords much better handling.  The sample head can be kept vertically with
the plates horizontal at all times.  The sample head is also clamped in place and
doesn't have to be threaded on to the probe, which avoids more handling.
     Isokinetic sampling rates can be determined more readily when the Andersen
is in the oven since the probe has a pi tot attached and the probe remains in the
stack (for in-stack sampling a pi tot measurement is made, the pi tot is removed
                                      -18-

-------
and the sampler is inserted to approximately the same position).  There are two
problems with sampling this way:  the oven can be heated only to 350°F, which
may not be as high as the temperature in the stack, and larger particles tend
to be deposited in the probe, which lowers the weight of the deposit on the first
two plates.
     Parallel sampling with both the Mark II plates above and the Mark III plates
with filters indicates that there isn't any significant difference in the weight
of catch and the size distribution between these two methods.  If the Mark II
model is used, the number of tests is limited by how many sets of plates are avail-
able.  With the Mark III plates and filters more runs can be performed by chang-
ing the filters between runs with the available time being the only constraint
on the number of runs.  More care must be taken in assembling the Mark III, since
the filters are pre-cut to match the plates and must be properly aligned to avoid
blocking any holes.
     As a result of these comparison tests, it was decided that testing would be
performed with the Mark III plates and filters and that the Andersen sample head
would be placed in the oven for ease in handling and subsequent analysis.
     Photomicrographs have been made by Illinois Institute of Technology Research
Institute (IITRI)  of samples collected on each stage from three Andersen runs.
These pictures confirm that the Andersen does in fact separate by particle size
as the instructions would indicate.   Evidence of this is shown in Figures  6,  7
and 8 from General Motors and Figures 9, 10, 11 and 12 from the Stag Brewery.
     Figure 6 is from stage 2 taken at 163x.  This shows a high percentage of
fly ash and partially fused clays and minerals, average particle size is approxi-
mately 6 microns.   Figure 7 is from stage 4 taken at 163x.  This shows much small-
er particles, a high percentage of fly ash and more Fe^CL, and an average
particle size of approximately 2 microns.  Figure 8 is from stage 6 taken  at 163x.
This shows mostly  submicron partially burned coal, fly ash and Fe20o-
     For spherical particles with unit density stage 2 should have separated
from 10.9 to 17 microns, stage 4 from 5.0 to 7.3 microns, and stage 6 from 1.7  to
3.2 microns.  Since fly ash has a density between 2 and 3, these stages will
actually separate  smaller particles.
                                     -19-

-------
FIGURE 6
                           DEPOSITS  ON  STAGES
                           2,4 AND 6
                           GENERAL MOTORS
FIGURE 8
 -20-

-------
-21-

-------
     Figure 9 from Stag Brewery is from stage 2 taken at 406x.   This shows lots
of incompletely combusted coal, partially fused glassy material  and Fe^O,
partially fused and coating other particles.   Average particle  size is approxi-
mately 5 microns.   Figure 10 is from stage 4  taken at 406x.   This shows fine fly
ash spheres most of which are dark due to iron in solid solution and some miner-
als and fine carbonaceous particles.  Average particle size is  approximately 2
microns.  Figure 11 is from stage 6 taken at  406x.  This shows  what appears to be
black carbonaceous material which hit as a liquid or is particles suspended in a
liquid.  There is  very little fly ash or else it is below 0.5 micron.  Figure 12
is from the backup filter taken at 406x.  This shows extremely  fine liquid drop-
lets with trapped  fine carbonaceous particles and extremely fine sulfate par-
ticles.
     Microscopic analysis of the filters has  indicated that sulfate crystals form
on the filters in  increasing amounts on descending stages to the point where the
backup filter sample is mostly sulfate.  Personnel from IITRI have indicated that
these crystals are ammonium sulfate and that  they have grown on the filters.
Figure 13 is from  a backup filter from a test at General Motors, taken at 163x.
Clearly, these crystals could not have passed through the Andersen impactor.
     The mechanism for the formation of these crystals is still  not understood.
Apparently, there  is a reaction between ammonia in the flue gases with sulfuric
acid on the filters.  To check that this reaction didn't take place from ex-
posure sometime later, one backup filter was  sealed in an air-tight enclosure at
the test site and  then examined immediately after opening the sample container.
This sample also showed a large amount of crystals.
     A few of these backup filters have been  analyzed for acidity.  Approximately
17% of the amount of sulfuric acid measured in the stack at General Motors.was
found to be entrained by the backup filter and by the total  particulate filter
on an EPA particulate run.  Whether this is due to condensation and entrainment,
or a gas-solid phase reaction, is not known.   At these temperatures, 440°F in-
stack and 350°F in the oven, sulfuric acid vapor should not condense.
     One test run  indicated that temperature has some relationship to the amount
of material in the backup  filter.  Two identical Andersen runs  were made at
General Motors with the sample head in the oven.  The first test was with an oven
                                    -22-

-------
        FIGURE 13
AMMONIUM SULFATE CRYSTALS
    ON BACK-UP FILTER
     GENERAL MOTORS
            -23-

-------
temperature of 300°F and  the second  with  a  temperature  of 370°F.   While  the  first
8 stages were very similar in weight,  there was  twice as  much  material collected
on the backup filter in the first test than in  the  second.
     The particle size distribution  from  all  of  the tests performed  to date  shows
a bimodal  distribution, generally with a  peak around stages  4  or  5 and a large
peak on the last backup stage.  A typical  curve  is  shown  in  Figure 14.   The  large
amount of sulfate crystals on the backup  indicates  that perhaps 30%  of that  amount
is sulfuric acid and should not be included.   But even  after this is subtracted
there are two peaks, one  around 5 microns  and the other less than 0.7 micron.
                                     -24-

-------
45-
40-
35-
30-
25-
20-
15-
10-
 5-
         FIGURE 14
PARTICLE SIZE  DISTRIBUTION
        WOOD RIVER
         BOILER #4
I
       11   10   987654    32    1    0
                            ECD, microns
                                 -25-

-------
                            5.0 REFERENCES

 1.   Llttman,  F.  E.,  "Regional  Air Pollution Study Point Source Methodology and
     Inventory"  Rockwell  International, EPA 450/3-74-054, October 1974
 2.   Littman,  F.  E. and  R.  W.  Griscom  "RAPS Point Source Emission Inventory - Phase
     II"  Air Monitoring  Center,  Rockwell  International, EPA Contract No. 68-02-
     1081,  July  1975.
 3.   Littman,  F.  E.,  R.  W.  Griscom and Otto Klein "RAPS Point Source Emission Inven-
     tory"  Air Monitoring Center, Rockwell International, EPA Contract No. 68-02-
     1081 ,  February 1976.
 4.   Pierre, John, and W.  Tillman "RAPS Point  Source  Emission Inventory  Data Hand-
     ling System" Air Monitoring Center,  Rockwell International, EPA Contract No.
     68-02-1081 ,  February 1976.
 5.   "Guide for  Compiling a Comprehensive Emission  Inventory", U. S. Environmental
     Protection  Agency APTD-1135, March 1973.
 6.   Corbett,  P.  F.,  "The SOo  Content  of  the Combustion Gases from an Oil-fired
     Water-tube  Boiler", J.  Inst. Fuel, Aug. 1953, p. 92.
 7.   Lee, G. K.  et al,  "Effect of Fuel Characteristics and Excess Combustion Oil  on
     Sulfuric  Acid Formation in a Pulverized-coal-fired Boiler", J.  Inst.  Fuel,
     Sept.  1967,  p. 397.
 8.   Lee, G. K.,  et al ,  "Control of  S03 in Low-pressure Boiler", J.  Inst.  Fuel,
     Feb.  1969,  p. 67.
 9.   Gills, B. G., "Production and Emission of Solids, SO, and NO,, from  Liquid  Fuel
     Flames, J.  Inst. Fuel, Feb. 1973, p. 71.
10.   Reese, J. T., et al, "Prevention  of  Residual Oil Combustion Problems  By Use
     of Low Excess Air", Trans.  ASME,  J.  Engrg.  Power, 1965, V87A, p. 229.
11.   Hamil, H. F., et al, "Collaborative  Study of EPA Method 8 (Determination of
     Sulfuric  Acid Mist  and Sulfur Dioxide Emissions  from Stationary Sources)",
     EPA 650/4-75-003.
                                      -26-

-------
12.  Hillenbrand,  et al,  "Chemical  Composition of Participate  Air  Pollutants  from
     Fossil-Fuel  Combustion Sources",  Battelle Columbus  Labs,  March  1973,  EPA-
     R2-73-216,  PB219.009.
13.  Goks0yr, H.,  and K.  Ross, "Determination of Sulphur Trioxide  in Flue  Gases",
     J.  Inst. Fuel  V35,  p.  177 (1962).
14.  Lisle, E.  S.  and J.  D. Sensenbaugh,  "Determination  of Sulfur  Trioxide and  Acid
     Dew Point in  Flue Gases", Combustion 36_, 12, (1965).
15.  Weast, T.  E.,  et al,  "Fine Particulate  Emission  Inventory and Control Survey",
     Midwest Research Institute, EPA 458/3-74-040,  Jan.  1974.
                                     -27-

-------
APPENDIX I
      -28-

-------
                         LABORATORY EVALUATION
                         OF THE "SHELL" METHOD
                                  OF
                         DETERMINATION OF SOg

     The "Shell" method for determination of sulfur trioxide (sulfuric acid)
in flue gas is based on its selective condensation from the flue gas.  This
is achieved by utilizing the relatively high (60-90°C) dew point of SO^.  At
this temperature only the sulfuric acid condenses from the flue gas and there-
fore it can be determined rather easily.
     Flue gas is drawn through the condenser at a rate of 2 liters per minute
for 10-20 minutes depending upon the SO, level  in the flue gas.  Particulates
are removed from the flue gas sample by using a plug of glass wool as a filter.
At the end of the sampling period, the H^SO* is washed out of the condenser
with 5% solution of isopropyl alcohol in water.  The combined washings were
titrated with 0.02 N NaOH using bromophenol blue as indicator.
     The laboratory evaluation of this method had a dual purpose.  The first
was to check the accuracy of the method under the experimental  conditions and
secondly, to determine which of the experimental parameters may affect the per-
formance of this method.  For the latter, stack conditions had  to be simulated
in a way which would allow adjustment of each parameter to predetermined levels,
The accuracy of the method was tested by duplicating the experimental  work of
                                                                         tio
                                                                         (2)
E.S.  Lisle and J.D.  Sensenbaugtv  .   The effect of the experimental  conditions
on the accuracy of the method was evaluated by using the Plackett-Burman
statistical design of screening process variables.  This method is based on
balanced incomplete blocks.  A good example of applying this method to a chem-
                                                            (3}
ical process has been published by R.A. Stowe and R.P. Mayerv '.  With this
method it is possible to effectively screen all the experimental parameters and
to find out which of them most likely will affect the overall process, by per-
forming only a small fraction of experimental work usually required for other
methods of screening variables.  For example, a complete factorial design for
fifteen variables at two levels requires 32,768 experiments; with the Plackett-
                                     -29-

-------
 Burman  method  the  same  number  of  variables  can  be  screened effectively with
                    (3)
 only 16 experiments   '.   It  should  be  emphasized,  however, that  this  method
 does not optimize  the process;  it only indicates which  of the  parameters  do
 not affect  the process.
 EXPERIMENTAL
      The experimental set-up used in this  study is given in  Figure  1.  A
 special  condenser  thermostated  at 60-90°C  was used for  the collection of  the
 condensed H^SO^.   The simulated flue gas  is introduced  at the  end of  the  con-
 denser  which consists of  a spiral glass tube followed by a coarse glass frit-
 ted disc.   Both the  spiral and  the  glass  fritted disc are kept at constant tem-
 perature (60-90°C)  by circulating water from a  heating  bath.   The H^SO, gener-
 ator consists  of a  quartz tubing  heated electrically by a spiral of nichrome
 wire insulated by  several layers  of asbestos tape.  With this  arrangement the
 temperature of the  hLSCL  generated  can be  adjusted at the desired level and  kept
 constant within 10°F.   Dilute  sulfuric acid solution is added  at a  constant  rate
 by a peristaltic pump through  a hypodermic  needle  and serum  cap  in  the top open-
 ing of  the  HUSO* generator.  The  rate  of  ^SO,  addition can  be altered by using
 pump tubes  of  different diameter. The  flow rate of the  gases (O^, N2, S02) was
 adjusted and maintained at the  proper  levels with  a combination  of  valves and
 rotometers.  The total  flow  was checked by a rotometer  at the  outlet  of the
 condenser.
 PROCEDURE
      The HUSO* generator  was calibrated by titrating the amount  of  acid delivered
 by the  peristaltic pump at the upper end  of the generator for  a  certain period
 of time (about 10  minutes) for the  two pump tubes  and the two  H?SO» solutions used
 throughout  the experimental  work. The  nominal flow rates of  the  pump  tubes used
 were 0.42 and  0.70 cc/min and  the normality of  the h^SO, solutions  was 0.01  and
 0.03 N.  Tables 1, 2,  3 and  4  give  the calibration of the HUSO,  generator for  the
 above flow  rates and the  sulfuric acid solutions.   The  results are  expressed in
 u. equiv/min.   The actual experiments  were conducted  in a similar manner. Sul-
furic acid solution was  delivered  to the HUSO, generator by the pump for about
ten minutes  and collected  in  the condenser.   The condensed hLSO*  was washed out
of the condenser with 5% isopropyl alcohol  in water and  the combined washings
                                       -30-

-------
 13
Q_


 o

-M _


 ra
 S-
 OJ
D_
                                                              CM
                                                                                               o
                                                                                               O
                                                                                               o
                                                                                               O
                                                                                                CM
          UJ
     uj   o:
     Oi   CO
     ID   t—i
     CD   _i
                                               -31-

-------
Table 1
CALIBRATION OF THE S03 GENERATOR


Run #
1
2
3
4
5



Time
Sec.
601.
599.
599.
600.
600.

Nominal Pump Rate =0.42
Normality of H^SO, Solution
cc of 0.02 N NaOH
7 2.58
7 2.42
5 2.45
3 2.30
4 2.32
Average
Table 2
cc/min
= 0.01 N
y equil/min
5.14
4.84
4.90
4.60
4.63
4.82 2: 0.22 y. equiv/min

CALIBRATION OF THE SO. GENERATOR
o


Run #
1
2
3
4


Time
Sec.
501 .
601 .
600.
600.
Nominal Pump Rate = 0.42
Normality of H2S04 Solution
ml of 0.2 N NaOH
0 7.46
5 7.82
4 7.52
5 7.66
cc/min
= 0.03 N
y equil/min
14.89
15.60
15.03
15.30
     Average        15.20 +_ 0.31 y. equiv/min
        -32-

-------
                  TABLE  3

      CALIBRATION OF THE S03 GENERATOR
       Nominal Pump Rate = 0.7U cc/min
     Normality of H2S04 Solution = 0.01  N

Time             Titrant
in #
1
2
3
4
5
Sec.
630.6
600.0
689.8
600.7
600.4
ml of 0.02 N NaOH
4.60
4.46
4.98
4.44
4.42
y equil/min
8.15
8.92
8.66
8.87
8.83
                       Average          8.81  t 0.10   y.equiv/min
                  TABLE 4

      CALIBRATION OF THE S03 GENERATOR
       Nominal  Pump Rate =  0.70  cc/min
     Normality  of H2S04 Solution =  0.03 N

in #
1
2
3
4
5
Time
Sec.
599.9
600.2
599.2
600.7
602.2
Titrant
cc of 0.02 N NaOH
12.80
12.23
12.26
12.42
13.24

y equil/min
25.60
24.45
24.55
24.81
26.38
                       Average          25.16 t  0.82  y.equiv/min
                              -33-

-------
were titrated with 0.02 N_ NaOH.   Throughout this work all  the experimental
parameters were varied at two levels:  one high level  and one low level  des-
ignated here as (+) or (-) respectively.   Table 5 gives all  the experimental
parameters examined in this study and  their respective high  and low values.
     The resulting efficiency of collection of the generated H?SO» vapors was
determined by dividing the recovered amount of H?S(L  by the  amount of SO^ de-
livered into the system (Tables  1 and  4).
RESULTS AND DISCUSSION
     As it was mentioned previously, the  purpose of this study was to first de-
termine the efficiency of the system under the recommended conditions and sec-
ondly to screen all the experimental parameters and determine which of them af-
fect the efficiency of the system.
     Table 6 summarizes the results obtained by using the system under the rec-
ommended conditions.  No SCL was used  in  these experiments because the main pur-
pose was to determine the efficiency of collection of H9SO,,  from flue gas.   These
                                                                             (1)
experiments were performed in the manner  recommended  by Lisle and Sensenbauglv  .
The samples were introduced in the evaporator by a syringe through the serum cap
without the use of the proportioning pump.  The average recovery was found to be
equal to 100.1 - 6.5%.  It should be noted, however,  that no extra effort was
made to optimize any of the experimental  conditions and therefore these results
represent data obtained by a casual application of this method.  A close inspec-
tion of the results tabulated in Table 6  shows that sources  of positive (recov-
eries > 100%) and negative (recoveries  < 100%) errors  do exist and therefore an
examination of the  parameters affecting  the accuracy of the method appeared  to
be  necessary.  The  parameters listed in  Table  5 were tested by the method  of
Plackett and  Burman by using a matrix for  sixteen runs and  fifteen variables.
Figure 2 gives the Plackett-Burman matrix used in this study.  Five out of the
fifteen variables were blank "dummy" tests from which the standard error of the
method was calculated.
     The statistical analysis of the results is given in Table 7.  In this table,
confidence levels are shown only to the 70% level; the remaining variables are
considered to have an insignificant effect on the method within the studied ranges,
Therefore from the ten variables studied  only four may have an effect on the ac-
                                     -34-

-------
                                TABLE 5

                      VARIABLES CHOSEN FOR STUDY

Code letter of                                                    Levels
the variable                   Variable                       Low(-)    High(+)

     A            Temperature of Condenser (°C)                60 i 3    90-3
     B            Temperature of Evaporator (°F)               550      650
     C            02/S02 Ratio                                149      223
    (D)           Dummy                                       —      —
     E            Total Flow (liter/min)                       2        4
     F            Flow Rate of H2S04 Solution (cc/min)         0.42     0.70
    (G)           Dummy                                       —      —
     H            Elapsed Time Prior to Rinsing  the           1        10
                  Condenser (min)
     I            Volume of Solvent for Each Washing  (ml)      10       25
     J            Total Volume of Solvent Used for Each        135      185
                  Experiment (ml)
     K            Size of Hypodermic Needle (gauge)           26       20
    (L)           Dummy                                       —      —
     M            Normality of H2S04 Solution                 0.01     0.03
    (N)           Dummy                                       —      —
    (0)           Dummy                                       —      —
                                     -35-

-------
                                 TABLE 6
                   COLLECTION EFFICIENCY  OF THE  METHOD
                   OF S03 DETERMINATION IN  FLUE  GASES
Volume of acid = 4.0 mil;  total  flow =  3.96 liter/min;  nitrogen  to  oxygen ratio
                            •e 85°C;  temporal
                            m.  equiv.  H?S04
20:1; condenser's temperature 85°C;  temperature  of H^SO,  generator 600°F
Run #
1
2
3
4
5
6
7
8
9
10
11
12
Taken
0.040
0.040
0.040
0.040
0.080
0.080
0.080
0.080
0.120
0.120
0.120
0.120
Found
0.039
0.042
0.041
0.047
0.077
0.077
0.074
0.077
0.123
0.119
0.120
0.115
% Recovet
97.50
105.00
102.50
117.50
96.25
96.25
92.50
96.25
102.50
99.17
100.00
95.83
                             Average % Recovery 100.0 +_ 6.5
                                   -36-

-------
                       PLACKETT-BURMAN MATRIX  FOR  DETERMINING
                          THE EFFECTS  OF  FIFTEEN VARIABLES
                          AT TWO LEVELS USING  SIXTEEN  RUNS
                                                              - = LOW
Random      Run                 Van'able                       + = "^
Number     Order    A  B  C   (D)   E   F   (G)   H   I  J   K   (L)   M  (N)  (0)   % Recovery

   1         1       +  +  +    +   _+_+   +  __   +    __    _        92i4
   2         2       +  +  +_+_    +   +_-+--_    +        93i9
   3         3       +  +  _    +   _+    +   _-  +   ___+    +        92.5
   4         8       +  _+_++_-   +  -__    +   -{-    +        94 j
   5         4       -  +  _    +   +_-+__-   +    +   +    +        87A
   6         6       +-+    +   -_    +   ___+   +    +   +    _        86.6
   7         9       _  +  +_-+___  +   +   +    +   -    +        83J
   8        12       +  +  _-+_-_   +  +   +   +    -+    -       109.3
   9        10       +__    +   _-_+   +  +   +-    +   _    +        87.3
  10        13       __+_-_    +   +   +  +-   +    _+    +       102.1
  11        14       _  +  ___+    +   +   +  -+-    +   +    -        83.7
  12        16       +___++    +   +_  +   -   +    +   _    -        95.4
  13         5       ___.    +   ++    +   _   +  _+   +    _-+        98.5
  14         7       __+    +   ++_+-  +   +__+    _       107.5
  15        11       -4--H4-+-    +   -   +  +--    +   -    -        81.8
  16        15       ____-_-----_--    -        84i3
                                     FIGURE 2
                                          -37-

-------


























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-------
curacy of the method and should be studied further for the optimization of the
total system.  These four variables are the temperature of the evaporator (B),
the total flow (E), the total  volume of washing solution (J) and the normality
of the HpSO* solution used (M).  It should be noted at this point that from these
four variables, the two (B and M) are very closely related with the experimental
conditions used for generating simulated flue gas in the laboratory and therefore
may not be associated with the application of the method in the determination of
SO^ in real  flue gas.  The other two (E and J) are associated with the method and
appear to be the most significant parameters which may affect the accuracy of the
SOo determination in flue gas.  The total  flow (parameter E) most likely affects
the condensation of S03 from the flue gas  and the total  volume of washing solu-
tion (parameter J) is related  with the efficient washing of the condensed H2S(L.
These two parameters are most  likely the ones on which proper attention should be
given in the application of this method for determination of SOo in flue gas.
                                    -39-

-------
                             REFERENCES





1.  E.S.  Lisle and J.D. Sensenbaugh, Combustion 36., 12  (1965).



2.  R.L.  Plackett and J.P. Burman, Biometrica 33_, 305  (1946).



3.  R.A.  Stowe and R.P. Mayer, Ind. and Eng. Chem. 58.,  36  (1966)
                                    -40-

-------
APPENDIX II
      -41-

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-------
                                   TEC  JICAL REPORT DATA
                            (Please read lum-u^ lions on the reierse be/ore completing/
1. REPORT NO.
  EPA-600/4-77-017
4. TITLE AND SUBTITLE
  REGIONAL AIR POLLUTION STUDY
  Sulfur Compounds and Particulate Size Distribution
  Inventory                        	
                                                         5. REPORT DATE
                                                           April 1977
                                                         6. PERFORMING ORGANIZATION CODE
                                                           3. RECIPIENT'S \CCESSIOf*NO.
7 AUTHOR(S)

Fred Littman,  Robert W. Griscom,  and  Harry Wang
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Air Monitoring Center
Rockwell  International
11640 Administration Drive
Creve Coeur,  MO 63141
                                                         10 PROGRAM ELEMENT NO.

                                                             1AA603
                                                         11. CONTRACT/GRANT NO.
                                                          68-02-1081
                                                          Task Order  56
12 SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory
Office  of  Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
                                            -  RTP, NC
                                                          13. TYPE OF REPORT AND PERIOD COVERED
                                                             Final
                                                         14. SPONSORING AGENCY CODE

                                                             EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
       In conjunction with  the  Regional Air Pollution  Study being conducted  in
  the St. Louis Air Quality Control Region  (AQCR), a methodology for estimating  the
  amount of sulfur trioxide (SO )  emitted by combustion  sources was developed.   It
  is based on SO /SO  ratios determined both experimentally and from literature
  surveys.  Th~ most likely value  appears to be 1.85%  of the SO,, emissions.   On
           fl-~ most l:kely value appears  to  be 1.85% of the SO  emissions.
this basis, about 22,000 tons of SO  are emitted yearly from combustion sources

     A fine particle size inventory for  the area was also developed.   The  inventory
gives a breakdown of particulate emissions  in the range of 7 to  .01  microns,
based on production rates and collection efficiencies for point  sources in the
St. Louis AQCR. The information on the SO /SO  ratios and the particle size
breakdown is stored in the RAPS Data Handling System.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                            b.IDENTIFIERS/OPEN ENDED TERMS  C. COSATI Field/Group
*Air pollution
*Sulfur  tiroxide
*Particle  size distribution
*Estimates
*Environmental surveys
                                             St.  Louis,  MO
13B
07B
05J
13. DISTRIBUTION STATEMENT


RELEASE  TO PUBLIC
                                            19. SECURITY CLASS (This Report)
                                              UNCLASSIFIED
21. NO. OF PAGES
      54
                                            20. SECURITY CLASS (This page!
                                             UNCLASSIFIED
                                                                         22. PRICE
EPA Form 2220-1 (9-73)
                                            46

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